Production of novel phosphane ligands and use in catalytical reactions

ABSTRACT

The invention relates to novel phosphane ligands of formula (Ia) and (Ib): (adamantyl)nP(alkyl)m(1a); (adamantyl)o(Alkyl)qP (alkylen′)P(adamantyl)r(alkyl)s (1b), wherein adamantyl represents an adamantyl radical (IIa, IIb) bonded to the phosphorous atom in position 1 or 2. The invention also relates to the production and use of the above-mentioned ligands in the presence of transitional metal compounds of the 8th. Subgroup of PSE for catalytic reactions, particularly for the refining of halogen aromatics for producing aryl olefins, dienes, diarylene, benzoic acid and acrylic acid derivatives, aryl alkanes and also amines.

DESCRIPTION

[0001] The present invention relates to novel phosphine ligands, totheir preparation and to their use in catalytic reactions, especiallyfor refining halogenoaromatics.

[0002] Halogenoaromatics, including especially chloroaromatics, areintermediates which have a variety of applications in the chemicalindustry and are used as precursors for the preparation of agriculturalintermediates, pharmaceuticals, dyestuffs, materials, etc. Vinyl halidesare also important intermediates which are used as precursors forpolymer monomers and the above-mentioned products.

[0003] Catalysts frequently used for the functionalization ofhalogenoaromatics or vinyl halides to give aromatic olefins or dienes(Heck reaction, Stille reaction), biaryls (Suzuki reaction), alkynes(Sonogashira reaction), carboxylic acid derivatives (Heck carbonylation)and amines (Buchwald-Hartwig reaction) are those of palladium andnickel. Palladium catalysts are generally advantageous in terms of thebreadth of applicability of coupling substrates and in some cases thecatalyst activity, while nickel catalysts have advantages in the area ofthe conversion of chloroaromatics and vinyl chlorides and the price ofthe metal.

[0004] Palladium and nickel catalysts used to activate and otherwiserefine halogenoaromatics are palladium(II) and/or nickel(II) as well aspalladium(0) and/or nickel(0) complexes, although it is known thatpalladium(0)/nickel(0) compounds are the actual reaction catalysts. Inparticular, according to literature sources, coordinatively unsaturated14-electron and 16-electron palladium(0)/nickel(0) complexes stabilizedwith donor ligands such as phosphines are formulated as active species.

[0005] It is also possible to dispense with phosphine ligands when usingiodides as educts in coupling reactions. However, aryl and vinyl iodidesare very expensive starting compounds and moreover producestoichiometric amounts of iodine salt waste. More cost-effective eductsfor the Heck reaction, such as aryl bromides or aryl chlorides, requirethe use of stabilizing and activating ligands in order to becomeeffective in catalytic production.

[0006] The catalyst systems described for olefinations, alkynylations,carbonylations, arylations, aminations and similar reactions often havesatisfactory catalytic turnover numbers (TONs) only with uneconomicstarting materials such as iodoaromatics and activated bromoaromatics.Otherwise, in the case of deactivated bromoaromatics and especially inthe case of chloroaromatics, it is generally necessary to add largeamounts of catalyst—usually more than 1 mol %—to achieve industriallyuseful yields (>90%). In addition, because of the complexity of thereaction mixtures, simple catalyst recycling is not possible, so therecycling of the catalyst also incurs high costs, which are normally anobstacle to realization on the industrial scale. Furthermore,particularly in the preparation of active substances or active substanceprecursors, it is undesirable to work with large amounts of catalystbecause of the catalyst residues left behind in the product. More recentactive catalyst systems are based on cyclopalladized phosphines (W. A.Herrmann, C. Brossmer, K. Öfele, C.-P. Reisinger, T. Priermeier, M.Beller, H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int. Ed.Engl. 1995, 34, 1844) or mixtures of sterically exacting arylphosphines(J. P. Wolfe, S. L. Buchwald, Angew. Chem. 1999, 111, 2570; Angew. Chem.Int. Ed. Engl. 1999, 38, 2413) or tri-tert-butylphosphine (A. F. Littke,G. C. Fu, Angew. Chem. 1998, 110, 3586; Angew. Chem. Int. Ed. Engl.1998, 37, 3387) with palladium salts or palladium complexes.

[0007] However, even with these catalysts, cost-effectivechloroaromatics cannot generally be activated satisfactorily from theindustrial point of view, i.e. catalyst productivities (TONs) are<10,000 and catalyst activities (TOFs) are <1000 h⁻¹. Therefore, toachieve high yields, it is necessary to use comparatively large andhence very expensive amounts of catalyst. Thus, for example, thecatalyst costs for the preparation of one kilogram of an organicintermediate with a molecular weight of 200, using 1 mol % of palladiumcatalyst, are more than 100 US$ at current noble metal prices, so thereis clearly a need for improving catalyst productivity. Therefore,despite all the catalyst developments in recent years, only a fewindustrial reactions have so far been disclosed for the arylation,carbonylation, olefination etc. of chloroaromatics.

[0008] For the reasons mentioned, the object of the present inventionwas to satisfy the great. need for novel, more productive catalystsystems which have simple ligands and do not exhibit the disadvantagesof the known catalytic processes, which are-suitable for the largeindustrial scale and which convert cost-effective chloroaromatics andbromoaromatics and corresponding vinyl compounds to the respectivecoupling products in high yield, with high catalyst productivity andwith high purity.

[0009] This object is achieved according to the invention by thedevelopment of novel phosphine ligands of formulae Ia and Ib:

(adamantyl)_(n)P(alkyl)_(m)   Ia

(adamantyl)_(o)(alkyl)_(q)P(alkylene′)P(adamantyl)_(r)(alkyl)_(s)   Ib

[0010] in which adamantyl is an adamantyl radical (IIa, IIb) bonded tothe phosphorus, atom. in the 1- or 2-position:

[0011] alkyl is a C₁ to C₁₈ alkyl group, and

[0012] alkylene′ is a bridging methylene, 1,2-ethylene, 1,3-propylene,1,4-butylene, 1,5-pentylene or 1,6-hexylene bridge, 1,2-diphenylene,2,2′-substituted 1,1′-binaphthyl or a ferrocenyl derivative,

[0013] where the alkyl group, the alkylene′ group and the adamantylradical independently of one another can have, in addition to hydrogenatoms, up to 10 substituents which independently of one another are C₁to C₈ alkyl, O-alkyl(C₁-C₈), OH, OCO-alkyl(C₁-C₈), O-phenyl, phenyl,aryl, fluorine, NO₂, Si-alkyl(C₁-C₈)₃, CN, COOH, CHO, SO₃H, NH₂,NH-alkyl(C₁-C₈), N-alkyl(C₁-C₈)₂, P(alkyl(C₁-C₈) )₂, P(aryl)₂,SO₂-alkyl(C₁-C₆), SO-alkyl(C₁-C₆), CF₃, NHCO-alkyl(C₁-C₄),COO-alkyl(C₁-C₈), CONH₂, CO-alkyl(C₁-C₈), NHCHO, NHCOO-alkyl(C₁-C₄)ICO-phenyl, COO-phenyl, CH═CH—CO₂-alkyl (C₁-C₈), CH═CHCOOH, PO(phenyl)₂,PO(alkyl(C₁-C₄))₂, PO₃H₂, PO(O-alkyl (C₁-C₆))₂ or SO₃(alkyl(C₁-C₄)),aryl being an aromatic with 5 to 14 ring carbon atoms and it beingpossible for one or more ring carbon atoms to be replaced by nitrogen,oxygen and/or sulfur atoms to give a 1- to 13-membered heteroaromaticcontaining ring carbon atoms,

[0014] where n is a number between 1 and 3 and m is a number between 0and 2, it being necessary to satisfy the condition n+m=3, and

[0015] where o and r are the number 1 or 2 and q and s are the number 0or 1, it being necessary to satisfy the conditions o+q=2 and r+s=2.

[0016] The phosphine ligands used according to the invention areespecially compounds of formulae Ia and Ib in which adamantyl is anadamantyl radical (IIa, IIb) bonded to the phosphorus atom in the 1- or2-position and alkyl is a C₁ to C₁₂ alkyl group. Alkylene′ is preferablya bridging 1,2-ethylene, 1,3-propylene or 1,4-butylene bridge,1,2-diphenylene, 2,2′-substituted 1,1′-binaphthyl or a ferrocenylderivative.

[0017] Preferably, the alkyl group, the alkylene′ group and theadamantyl radical independently of one another can-have, in addition tohydrogen atoms, up to 5 substituents which independently of one anotherare C₁ to C₈ alkyl, O-alkyl(C₁-C₈), OH, OCO-alkyl(C₁-C₈), O-phenyl,phenyl, aryl, fluorine, Si-alkyl(C₁-C₈)₃, COOH, SO₃H, NH₂,NH-alkyl(C₁-C₈), N-alkyl₂(C₁-C₈), P(alkyl(C₁-C₈))₂, P(phenyl)₂, CF₃,NHCO-alkyl(C₁-C₄), COO-alkyl(C₁-C₈), CONH₂, CO-alkyl(C₁-C₈), COO-phenyl,PO(phenyl)₂, PO(alkyl(C₁-C₄))₂, PO₃H₂or PO(O-alkyl (C₁-C₆))₂, aryl beingan aromatic with 5 to 14 ring carbon atoms and it also being possiblefor one or more ring carbon atoms to be replaced by heteroatoms from thegroup comprising nitrogen, oxygen and sulfur atoms to give aheteroaromatic with 4 to 13 ring carbon atoms.

[0018] Heteroaromatic radicals can be e.g. at least five-membered ringscontaining 1 to 13 ring carbon atoms and up to 4 nitrogen atoms and/orup to 2 oxygen or sulfur atoms. Preferred heteroaromatic-aryl radicalscontain one or two nitrogen heteroatoms or one oxygen heteroatom or onesulfur heteroatom or one nitrogen heteroatom and one oxygen heteroatomor sulfur heteroatom.

[0019] Particularly preferred phosphine ligands according to theinvention are compounds of formulae Ia and Ib in which adamantyl is anadamantyl radical (IIa, IIb) bonded to the phosphorus atom in the 1- or2-position, alkyl is a C₁ to C₁₂ alkyl group and alkylene′ in formula Ibis a bridging 1,2-ethylene, 1,3-propylene or 1,4-butylene bridge, wherethe alkyl group, the alkylene′ group and the adamantyl radicalindependently of one another can have, in addition to hydrogen atoms, upto 3 substituents which independently of one another can be C₁ to C₈alkyl, O-alkyl(C₁-C₈), OH, OCO-alkyl(C₁-C₈), O-phenyl, phenyl, COOH,SO₃H, NH₂, P(alkyl(C₁-C₈))₂, P(phenyl)₂, COO-alkyl(C₁-C₈), CONH₂ or PO(phenyl)₂.

[0020] The invention also provides the preparation of the novelphosphine ligands. They are synthesized analogously to known preparativeroutes for alkylphosphines. Such synthetic pathways are described forexample in Houben-Weyl, Methoden der organischen Chemie, 1963, volumeXII, 1, p. 33. In general, the novel phosphine ligands described hereare prepared by reacting a dihalogenoadamantyl-phosphine orhalogenodiadamantylphosphine with metal-organic reagents (for examplealkyllithium, alkylmagnesium, alkylzinc or alkylcopper reagents).Particularly suitable halogenoadamantylphosphines are the correspondingchlorine compounds. Another synthetic route for the preparation of theligands according to the invention is to react alkali metaladamantylphosphides or alkali metal diadamantylphosphides with organicelectrophiles such as alkyl halides or pseudohalides, aldehydes orepoxides.

[0021] In general, diadamantylalkylphosphines can be synthesizedaccording to the following instructions: A solution of 18 mmol of R-M inTHF or hexane is added dropwise to a solution of 15 mmol ofdiadamantylchloro-phosphine in 250 ml of absolute THF, M being lithiumor MgHal and Hal being chlorine, bromine or iodine. The mixture isrefluxed for two hours. It is worked up at room temperature withdegassed aqueous ammonium chloride solution and diethyl ether. Thesolvents are distilled off and the residue is distilled under highvacuum or chromatographed on silica gel 60 with hexane/ethyl acetatemixtures.

[0022] These instructions can be used to prepare e.g. the followingpreferred ligands:

[0023] di(1-adamantyl)methylphosphine,

[0024] di (1-adamantyl)-i-propylphosphine,

[0025] di(1-adamantyl)-n-butylphosphine,

[0026] di(1-adamantyl)-t-butylphosphine,

[0027] di(1-adamantyl)-n-hexylphosphine,

[0028] di(1-adamantyl)cyclohexylphosphine,

[0029] di(1-adamantyl)benzylphosphine,

[0030] di(1-adamantyl)pentafluoroethylphosphine,

[0031] di(3-aminoadamant-1-yl)-n-butylphosphine,

[0032] di(3-acetyladamant-1-yl)-n-butylphosphine,

[0033] di[3-(p-hydroxyphenyl)adamant-1-yl]methylphosphine,

[0034] di(2-adamantyl)-i-propylphosphine,

[0035] di(2-adamantyl)-n-butylphosphine,

[0036] di(2-adamantyl)-t-butylphosphine,

[0037] di(2-adamantyl)cyclohexylphosphine.

[0038] In general, adamantyldialkylphosphines can be synthesizedaccording to the following instructions: A solution of 15 mmol of adialkylchlorophosphine in THF is added dropwise to a solution of 35 mmolof adamantyl-M in 400 ml of absolute THF or hexane, M being lithium orMgHal and Hal being chlorine or bromine. The mixture. is refluxed forfour hours. It is worked up at room temperature with degassed aqueousammonium chloride solution and diethyl ether. The solvents are distilledoff and the residue is distilled under high vacuum or chromatographedon, silica gel 60 with hexane/ethyl acetate mixtures.

[0039] These instructions can be used to prepare e.g. the followingpreferred ligands:

[0040] (1-adamantyl)di-t-butylphosphine,

[0041] (1-adamantyl)dicyclohexylphosphine,

[0042] (2-adamantyl)di-n-butylphosphine.

[0043] In general, bis(diadamantylphosphino)alkanes can be synthesizedaccording to the following instructions: A solution of 15 mmol ofM-alkylene-M in THF or hexane is added dropwise to a solution of 33 mmolof diadamantyl-chlorophosphine in 400 ml of absolute THF, M beinglithium or MgHal and Hal being chlorine, bromine or iodine. The mixtureis refluxed for four hours. It is worked up at room temperature withdegassed aqueous ammonium chloride solution and diethyl ether. Thesolvents are distilled off and the residue is distilled under highvacuum-or chromatographed on silica gel 60 with hexane/ethyl acetatemixtures.

[0044] These instructions can be used to prepare e.g. the followingpreferred ligands:

[0045] 1,2-bis[di(l-adamantyl)phosphino]ethane,

[0046] 1,4-bis[di(l-adamantyl)phosphino]butane,

[0047] 2,3-bis[di(l-adamantyl)phosphino]butane,

[0048]4,5-bis[di(l-adamantyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxolane,

[0049] 1,2-bis[di(l-adamantyl)phosphino]benzene.

[0050] According to the invention, the novel phosphine ligands are usedas catalysts in combination..with transition metal complexes ortransition metal salts of subgroup VIII of the Periodic Table of theElements, for example palladium, nickel, platinum, rhodium, iridium,ruthenium or cobalt. As a rule, the ligands according to the inventioncan be added in situ to appropriate transition metal precursor compoundsand used in this form for catalytic applications.

[0051] The transition metal compounds used are preferably palladium ornickel compounds and particularly preferably palladium compounds.

[0052] It may be advantageous on occasion to prepare defined mono-, di-,tri- or tetraphosphine complexes of said transition metals first andthen use these for catalytic. reactions.

[0053] It is preferable to use palladium and nickel catalysts containingthe phosphines according to the invention.

[0054] It is particularly preferable to use palladium catalystscontaining the ligands according to the invention. The ligands accordingto the invention are normally added in situ to palladium(II) salts or topalladium(II) or palladium(0) complexes. However, it may be advantageousto prepare palladium(0)—or palladium(II)-phosphine complexes of thephosphines according to the invention direct and then use these forcatalytic applications. This increases the initial catalyst activity insome instances.

[0055] Examples of palladium components that can be used with theligands according to the invention are palladium(II) acetate,palladium(II) chloride, palladium(II) bromide, lithiumtetrachloropalladate (II), palladium (II) acetylacetonate,palladium(0)-dibenzylidenacetone complexes, palladium(0)tetrakis(triphenylphosphine), palladium(0) bis(tri-o-tolylphosphine),palladium(II) propionate, palladium(II) bis(triphenylphosphine)dichloride, palladium(0)-diallyl ether complexes, palladium(II) nitrate,palladium(II) chloride. bis(acetonitrile), palladium(II) chloridebis(benzonitrile) and other palladium(0) and palladium(II) complexes.

[0056] Generally, for catalytic applications, the phosphine ligand isused in excess relative to the transition metal. The ratio of transitionmetal to ligand is preferably from 1:1 to 1:1000. Ratios of transitionmetal to ligand of 1:1 to 1:100 are particularly preferred. The exacttransition metal/ligand ratio to be used depends on the specificapplication and also on the amount of catalyst used. Thus, in general,it is conventional to use low transition metal/ligand ratios in the caseof very low transition metal concentrations (<O.01 mol %) than in thecase of transition metal concentrations of between 0.5 and 0.01 mol % oftransition metal.

[0057] The novel phosphine ligands are thermally very stable. It. isthus possible to use the catalysts according to the invention atreaction temperatures of up to 250° C. or more. The catalysts arepreferably used at temperatures of 20 to 200° C.; it has provedadvantageous in many cases to work at temperatures of 30 to 180° C.,preferably of 40 to 160° C. The ligands can also be used in pressurereactions without loss of activity, the operating pressureconventionally being up to only 100 bar, but preferably in the normalpressure range of up to 60. bar.

[0058] The phosphine ligands prepared according to the invention haveproved particularly advantageous as ligand components for the catalyticpreparation of arylated olefins (Heck reactions), biaryls (Suzukireactions), α-aryl ketones and amines from aryl halides or vinylhalides. However, it is obvious to those skilled in the art. that othertransition metal-catalyzed reactions, such as the metathesis orhydrogenation of double bonds or carbonyl compounds, especially howeverpalladium-catalyzed and nickel-catalyzed carbonylations of aryl halides,alkynylations with alkynes (Sonogashira couplings) and cross couplingswith metal-organic reagents (zinc reagents, tin reagents, etc.), canalso be catalyzed with the novel catalyst systems.

[0059] For some catalytic applications, for example carbonylations, itmay be advantageous to use chelating phosphine ligands, particularlyimportant chelating phosphine ligands being those with an aliphatic C₂to C₆ carbon bridge or with an aromatic bridge (1,2-phenylene,ferrocenyl, binaphthyl).

[0060] One particular advantage of the ligands according to theinvention is the high activity which the ligands induce in theactivation of cost-effective but inert chloroaromatics. As shown in theexperimental Examples, palladium catalysts with the noveladamantylphosphines are significantly superior to the best existingcatalyst systems of Buchwald (J. P. Wolfe, S. L. Buchwald, Angew. Chem.1999, 111, 2570; Angew. Chem. Int. Ed. Engl. 1999, 38, 2413) and Fu (A.F. Littke, G. C. Fu, Angew. Chem. 1998, 110, 3586; Angew. Chem. Int. Ed.Engl. 1998, 37, 3387). Thus, with the catalyst systems according to theinvention, it is even possible to achieve turnover numbers in the orderof >10,000 with chloroaromatics as substrates and TONs of >500,000 withbromoaromatics as starting materials, making the described catalyst andligand systems useful for large-scale industrial purposes.

[0061] The properties of the adamantylphosphines are particularlysurprising. Although adamantyl radicals have been known for a long timein organic chemistry, no importance has been attached to phosphineligands containing adamantyl groups. Consequently,alkyladamantylphosphines have not hitherto been described for catalyticapplications. It was surprising to find that, in certain catalyticapplications, adamantyl ligands are significantly superior to all otherknown phosphine ligands. For example, whereas the product yieldsobtained in the coupling of 4-chlorotoluene with an arylboronic acidusing small amounts of catalyst (0.005 mol %) are 16 to 46% with thebest palladium catalysts known hitherto, yields of >90% were obtainedwith the ligands according to the invention.

[0062] The phosphines prepared according to the invention can be usedfor the preparation of arylolefins, dienes, diaryls, benzoic acidderivatives, acrylic acid derivatives, arylalkanes, alkynes and amines.The compounds prepared in this way can be used inter alia as UVabsorbers, intermediates for pharmaceuticals and agrochemicals, ligandprecursors for metallocene catalysts, perfumes, active substances, andstructural units for polymers.

EXAMPLES

[0063] The Examples which follow serve to illustrate the inventionwithout implying a limitation.

[0064] General: The adamantylphosphine ligands are prepared under aprotective gas (argon).

[0065] General instructions for synthesis of the phosphines:

[0066] A mixture of 100 g (0.73 mol) of adamantane, 105 g (0.79 mol) ofaluminium(III) chloride and 300 ml of phosphorus(III) chloride wasrefluxed for 5 h. The excess phosphorus(III) chloride was distilled offto leave a reddish-brown viscous substance. This was suspended in 1 1 ofchloroform and then hydrolyzed with 1 1 of ice-water. The organic phasewas dried over sodium sulfate and concentrated to dryness under vacuum(0.1 mbar). Yield: 130 g (0.37 mol, 93%) of di(1-adamantyl)phosphinylchloride (melting point: 195° C.).

[0067] 40 g of diadamantylphosphinyl chloride (0.11 mol) were placed in600 ml of absolute tetrahydrofuran, the mixture was cooled to −14° C.with an ice-water/sodium chloride cooling mixture, and 10 g (0.26 mol)of lithium aluminium hydride were added in successive portions over 60min. The mixture was then stirred at room temperature for 16 h andhydrolyzed at −14° C. with 200 ml of 1 N HCl solution. The organic phasewas dried over sodium sulfate and concentrated to dryness under vacuum(0.1 mbar). Yield: 30 g (0.10 mol, 94%) of di(l-adamantyl)phosphine.

[0068]³¹P NMR (162.0 MHz, CDCl₃): δ=18.2

[0069] 60 g of a 20% solution of phosgene in absolute toluene were addeddropwise at −14° C. to a solution of 23 g (76 mmol) ofdi(1-adamantyl)phosphine and 14.5 g (9.5 mmol) of1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in 600 ml of toluene and themixture was heated to room temperature and then stirred for 16 h. It wasfiltered and the solvent was distilled off under vacuum. Yield: 23 g (68mmol, 90%) of diadamantylchlorophosphine.

[0070]³¹P NMR (162.0 MHz, CDCl₃): δ=138.4

Example 1

[0071] Di (1-adamantyl)-n-butylphosphine (n-BuPAd₂) (Variant 1):

[0072] 11 ml of a 1.6 M solution of n-butyllithium in hexane (18 mmol)were added dropwise to 5.0 g (15 mmol) of diadamantylchlorophosphine in250 ml of absolute tetrahydrofuran. The solution was refluxed for 1 h.After removal of the solvent under vacuum, the residue was distilledunder vacuum.

[0073] 2.6 g (7.3 mmol, 49%) of diadamantyl-n-butylphosphine wereobtained.

[0074] Di(1-adamantyl)-n-butylphosphine (n-BuP(1-Ad)₂) (Variant 2):

[0075] 4.6 g (15 mmol) of di(1-adamantyl)phosphine were placed in 50 mlof di-n-butyl ether, and 20 ml of a 2.5 M solution of n-BuLi in toluene(50 mmol) were added. The mixture was refluxed for 1 h and cooled and4.1 g (30 mmol) of 1-butyl bromide were added dropwise. The mixture wasrefluxed for 30 min, cooled and washed with saturated ammonium chloridesolution (3×), the organic phase was separated off and dried over sodiumsulfate and the solvent was distilled off under reduced pressure.

[0076] Yield: 4.6 g (13 mmol, 85%) of di(1-adamantyl)-n-butylphosphine.The product can be recrystallized from di-n-butyl ether (m.p.: 102° C.).

[0077]³¹P{¹H} NMR (162.0 MHz, C₆D₆, 297 K): δ=24.6

[0078] MS (E. I., 70 eV):. m/z: 358 (M⁺, 12%); 135 (Ad⁺, 100%)

[0079] MS (C.I., isobutene): m/z: 359 (M⁺+H, 100%)

[0080] Di(1-adamantyl)-n-butylphosphine (n-BuP(1-Ad)₂) (Variant 3):

[0081] 1.5 g (4.5 mmol) of di(1-adamantyl)chlorophosphine were placed in40 ml of absolute THF, and 5.ml of a 1.6 M solution of n-BuLi in hexane(8 mmol) were added using a syringe, with stirring. The mixture wasrefluxed for 2 h, the solvent was distilled off under reduced pressureand the residue was distilled in a bulb tube. Yield: 0.77 g (2.1 mmol,48%) of di(1-adamantyl)-n-butylphosphine.

[0082] Di(1-adamantyl)-n-butylphosphine (n-BuP(1-Ad)₂) (Variant 4):

[0083] 4.6 g (15 mmol) of di(1-adamantyl)phosphine were placed in 50 mlof di-n-butyl ether, and 20 ml of a 2.5 M solution of n-BuLi in toluene(50 mmol) were added. The mixture was refluxed for 1 h and cooled and2.8 g (30 mmol) of 1-butyl chloride were added dropwise. The mixture wasrefluxed for 30 min, cooled and washed with saturated ammonium chloridesolution (3×), the organic phase was separated off and dried over sodiumsulfate and the solvent was distilled off under reduced pressure. Theproduct was purified by bulb tube distillation under fine vacuum. Yield:4.6 g (13 mmol, 85%) of di(1-adamantyl)-n-butylphosphine.

Example 2

[0084] Di(1-adamantyl)methylphosphine (MeP(1-Ad)₂) (Variant 1):

[0085] 11 ml of a 1.6 M solution of methyllithium in hexane (18 mmol)were added dropwise to 5.0 g (15 mmol) of diadamantylchlorophosphine in250 ml of absolute tetrahydrofuran. The solution was refluxed for 1 h.After distillation of the solvent under vacuum, the residue wasdistilled under vacuum.

[0086] 2.3 g (7.3 mmol, 49%) of diadamantylmethylphosphine wereobtained.

[0087] Di(1-adamantyl)methylphosphine (MeP(1-Ad)2) (Variant 2):

[0088] 2.0 g (6.0 mmol) of di(1-adamantyl)chlorophosphine were placed in50 ml of absolute THF, and 5 ml of a 1.6 M solution of MeLi in diethylether (8 mmol) were added using a syringe, with stirring. The mixturewas refluxed for 2 h, the solvent was distilled off under reducedpressure and the residue was distilled in a bulb tube. Yield: 0.85 g(2.7 mmol, 45%) of di(1-adamantyl)methylphosphine (m.p.: 143° C.).

[0089] Elemental analysis: found (calc.): C: 79.52% (79.70%); H: 10.60%(10.51%); P: 9.78% (9.79%)

[0090]³¹P{¹H} NMR (162.0 MHz, C₆D₆, 297 K): δ=7.8

[0091] MS (E.I., 70 eV): m/z: 316 (M⁺, 36%); 135 (Ad⁺, 100%)

Example 3

[0092] Di(1-adamantyl)-n-hexylphosphine (HexP(1-Ad)₂) (Variant 1):

[0093] 0.45 g of magnesium turnings (18 mmol) was placed in 150 ml ofabsolute tetrahydrofuran, and 3.0 g of 1-bromohexane (18 mmol) wereadded, with stirring, causing the ether to warm up. After the mixturehad-cooled to room temperature, a solution of 5.0 g ofdiadamantylchlorophosphine (15 mmol) in 100 ml of absolutetetrahydrofuran was added dropwise and the mixture was refluxed for 1 h.After distillation of the solvent under vacuum, the residue wasdistilled under high vacuum (0.01 mbar). Yield: 2.0 g (5.2 mmol, 35%) ofdiadamantyl-n-hexylphosphine.

[0094] Di(1-adamantyl)-n-hexylphosphine (HexP(1-Ad)2) (Variant 2):

[0095] 5.5 g (18 mmol) of di(1-adamantyl)phosphine were placed in 60 mlof di-n-butyl ether, and 20 ml of a 2.5 M solution of n-BuLi (50 mmol)in toluene were added. The mixture was refluxed for 45 min and cooledand 3.0 g (18 mmol) of 1-bromohexane were added dropwise. The mixturewas refluxed for 30 min, cooled and washed with saturated ammoniumchloride solution (3×), the organic phase was separated off and driedover sodium sulfate and the solvent was distilled off under reducedpressure.

[0096] Yield: 4.9 g (13 mmol, 70%) of di(l-adamantyl)-n-hexylphosphine.The product can-be recrystallized from di-n-butyl ether.

[0097]³¹P{¹H} NMR (162.0 MHz, C₆D₆, 297 K): δ=24.6

[0098] MS: 386.31062 (calc. for C₂₆H₄₃P: 386.31024)

Example 4

[0099] Bis (diadamantylphosphino) butane (butylene (PAd₂) 2):

[0100] 0.45 g of magnesium turnings (18 mmol) was placed in 150 ml ofabsolute tetrahydrofuran, and 2.0 g of 1,4-dibromobutane (9.3 mmol) wereadded, with stirring, causing the ether to warm up. After the mixturehad cooled to room temperature, a solution of 5.0 g ofdiadamantylchlorophosphine (15 mmol) in 100 ml of absolutetetrahydrofuran was added dropwise and the mixture was refluxed for 1 h.After distillation of the solvent under vacuum, the residue wasdistilled under high.vacuum (0.01 mbar). Yield: 1.0 g (1.5 mmol, 10%) ofbis(diadamantylphosphino)butane.

Example 5

[0101] Di(1-adamantyl)-3-dimethylaminopropylphosphine:

[0102] 5.1 g (17 mmol) of di(1-adamantyl)phosphine were placed in 50 mlof di-n-butyl ether, and 20 ml of a 2.5 M solution of n-BuLi (50 mmol)in toluene were added. The mixture was refluxed for 1 h and cooled and5.0 g (31 mmol) of 3-dimethylaminopropyl chloride hydrochloride wereadded, with cooling in an ice bath. The mixture was refluxed for 30 min,cooled and washed with saturated ammonium chloride solution (3×), theorganic phase was separated off and dried over sodium sulfate and thesolvent was distilled off. under reduced pressure. Yield: 4.6 g (12mmol, 70%) of di(1-adamantyl)-3-dimethylaminopropylphosphine. Theproduct can be recrystallized from di-n-butyl ether (m.p.: 138° C.).

[0103] Elemental analysis: found (calc.): C: 77.46% (77.47%); H: 11.09%(10.92%); N: 3.47% (3.61%); P: 7.78% (7.99%)

[0104]³¹P{¹H} NMR (162.0 MHz, C₆D₆, 297 K): δ=24.5

[0105] MS: 387.30528 (calc. for C₂₅H₄₂NP: 387.30548)

Example 6

[0106] Di (1-adamantyl)benzylphosphine:

[0107] 4.0 g (13 mmol) of di(1-adamantyl)phosphine were placed in 50 mlof di-n-butyl ether, and 18 ml of a 2.5 M solution of n-BuLi (45 mmol)in toluene were added. The mixture was refluxed for 30 min and cooledand 3.2 g (19 mmol) of benzyl bromide were added dropwise. The mixturewas refluxed for 30 min, cooled and washed with saturated ammoniumchloride solution (3×), the organic phase was separated off and driedover sodium sulfate and the solvent was distilled off under reducedpressure. Yield: 4.6 g (12 mmol, 90%) of di(1-adamantyl)benzylphosphine.The product is recrystallized from di-n-butyl ether (m.p.: 182° C.)

[0108]³¹P{¹H} NMR(162.0 MHz, C₆D₆, 297 K): δ=29.8

[0109] MS: 392.26420 (calc. for C₂₇H₃₇P: 392.26328)

Examples 7 to 20

[0110] General Operating Instructions for the Heck Reaction:

[0111] In a pressure tube (obtainable e.g. from Aldrich), 5 mmol of arylhalide, 6 mmol of olefin, 6 mmol of base, a suitable amount of ligandand palladium(0)-dba complex and 500 mg of diethylene glycol di-n-butylether (as internal standard for GC analysis) were added to 5 ml ofabsolute dioxane under an argon atmosphere. The tube was sealed andsuspended in a silicone oil bath at 120° C. After 24 h it was left tocool to room temperature. The solids were dissolved in 5 ml of methylenechloride and 5 ml of 2 N hydrochloric acid. The organic phase wasanalyzed by gas chromatography. The products were isolated bydistillation, crystallization from methanol/acetone mixtures or columnchromatography (silica gel, hexane/ethyl acetate mixtures). TABLE 1 Heckreaction of p-chlorotoluene and styrene; n-BuPAd₂ as ligand Temp. Cat.conc. Conversion Yield No. Base (° C.) (mol %) L:Pd (%) (%) TON 7 K₃PO₄100 1.0 1:1 42 38 38 8 K₃PO₄ 100 1.0 2:1 39 25 25 9 K₃PO₄ 120 0.1 2:1 2720 200 10 K₃PO₄ 120 1.0 2:1 98 98 98 11 K₃PO₄ 120 0.1 4:1 25 11 110 12K₂CO₃ 120 1.0 2:1 78 68 68 13 K₃PO₄ 140 0.1 4:1 88 81 810

[0112] TABLE 2 Heck reaction of chlorobenzene and styrene at 120° C.;L:Pd = 2:1 Cat. conc. Conversion Yield No. Base (mol %) (%) (%) TON 14K₂CO₃ 1.0 71 63 63 15 K₃PO₄ 2.0 46 33 17

[0113] TABLE 3 Heck reaction with 2-ethylhexyl acrylate at 120° C.;base: K₃PO₄; 2.0 mol% of Pd (dba)₂; L:Pd = 2:1 No. Aryl chloride LigandConversion (%) Yield (%) TON 16

n-BuPAd₂ 66 63 32 17

n-BuPAd₂ 94 82 41 18

n-BuPAd₂ 51 34 17 19

n-BuPAd₂ 38 12 6 20

n-BuPAd₂ 48 44 22

Examples 21 to 40

[0114] General Operating Instructions for the Suzuki Reaction:

[0115] In a pressure tube (obtainable e.g. from Aldrich), 3 mmol of arylhalide, 4.5 mmol of phenylboronic acid, 6 mmol of base, a suitableamount of ligand and palladium(II) acetate (P:Pd=2:1) and 100 mg ofhexadecane (as internal standard for GC analysis) were dissolved in 6 mlof absolute toluene under an argon atmosphere. The tube was sealed andsuspended in a-silicone oil bath at 100° C. After 20 h it was left tocool to room temperature. The solids were dissolved in 10 ml ofmethylene chloride and 10 ml of dilute sodium hydroxide solution. Theorganic phase was analyzed by gas chromatography. The products wereisolated by crystallization from methanol/acetone mixtures or columnchromatography (silica gel, hexane/ethyl acetate mixtures). TABLE 4Influence of the ligand on the coupling of 4-chlorotoluene andphenylboronic acid No. PR₃ Pd(OAc)₂ (mol %) Yield (%) TON 21 PPh₃ 0.1 550 22 PhPCy₂ 0.1 23 230 23^([a]) (o-tol) PCy₂ 0.1 49 490 24^([a])(o-anisyl) PCy₂ 0.1 42 420 25 (o-biph) PCy₂ 0.01 47 4700 26 PCy₃ 0.1 23230 27 PtBu₃ 0.01 92 9200 28 P^(t)Bu₃ 0.005 41 8200 29 BuPAd₂ 0.01 949400 30 BuPAd₂ 0.005 87 17,400

[0116] TABLE 5 Suzuki coupling of various aryl chlorides (R-C₆H₄—Cl)with phenylboronic acid in the presence of 0.005 mol % of Pd(OAc)₂/2BuPAd₂ No. R Yield (%) TON 31 4-Me 87 17,400 32^([a]) 4-Me 74 14,800 332-Me 85 17,000 34 2,6-Me2 68 13,600 35 H 80 16,000 36 2-F 96 19,200 374-MeO 64 12,800 38 3-MeO 58 11,600 39 2-CN 100 20,000 40 “3-N,”^([b]) 9919,800

Examples 41 to 54

[0117] General Operating Instructions for Catalytic Amination:

[0118] In a pressure tube (obtainable e.g. from Aldrich), 5 mmol of arylhalide, 6 mmol of amine, 6 mmol of sodium tert-butylate and a suitableamount of ligand and palladium(0)-dibenzylidenacetone complex were addedto 5 ml of absolute toluene under an argon atmosphere. The tube wassealed and suspended in a silicone oil bath at 120° C. After 20 h it wasleft to cool to room temperature. The solids were dissolved in 5 ml ofCH₂Cl₂ and 5 ml of 2 N hydrochloric acid, and 500 mg of diethyleneglycol di-n-butyl ether were added as internal GC standard. The organicphase was analyzed by gas chromatography. The products were isolated bydistillation, crystallization from methanol/acetone mixtures or columnchromatography (silica gel, hexane/ethyl acetate mixtures). TABLE 6Catalytic amination of aryl halides; 0.5 mol % of Pd(dba)₂, n-BuPAd₂Yield No. Aryl chloride Amine Product [%] 41 2-chloro- 2, 6-bis(2,6-dimethyl- 84 m-xylene dimethylaniline phenyl) amine 42 2-chloro-2,6-diiso- 2,6-dimethylphenyl- 70 m-xylene propylaniline2′,6′-diisopropyl- aniline 43 2-chlorofluoro- 2,6-diiso- 2-fluorophenyl-70 benzene propylaniline 2′,6′-diisopropyl- aniline 44 2-chloro-1-adamantyl- N-(1-adamantyl)- 84 m-xylene amine 2,6-dimethylaniline 452-chloro- tert-butylamine N-(tert-butyl)-2,6- 93 m-xylene dimethylamine46 chlorobenzene diethylamine N,N-diethylaniline 44 47 chlorobenzenedi-n-butylamine N,N-di-n- 72 butylaniline 48 3-chlorotoluenediethylamine N,N-diethyl-m- 49 toluidine 49 3-chloroanisole diethylamineN,N-diethyl-m- 58 methoxyaniline 50 4-chlorotoluene diethylamineN,N-diethyl-p- 40 toluidine 51 chlorobenzene piperidineN-phenylpiperidine 76 52 chlorobenzene morpholine N-phenylmorpholine 8753 o-chloroanisole 2,6-dimethyl- 2-methoxyphenyl- 100 aniline2,6-dimethylaniline 54 o-chloroanisole 2,6-diiso- 2-methoxyphenyl- 88propylaniline 2,6-diisopropyl- aniline

Examples 55 to 59

[0119] Catalytic α-arylation of Ketones:

[0120] In a pressure tube (obtainable e.g. from Aldrich), 5 mmol of arylhalide, 6 mmol of ketone, 6 mmol of sodium tert-butylate and a suitableamount of ligand and palladium(II) acetate were added to 5 ml ofabsolute toluene under an argon atmosphere. The tube was sealed andsuspended in a silicone oil bath at 80° C. After 20 h it was left tocool to room temperature. The solids were dissolved in 5 ml of CH₂Cl₂and 5 ml of 2 N hydrochloric acid, and 500 mg of diethylene glycoldi-n-butyl ether were added as internal GC standard. The organic phasewas analyzed by gas chromatography. The products were isolated bydistillation, crystallization from methanol/acetone mixtures or columnchromatography (silica gel, hexane/ethyl acetate mixtures). TABLE 7Catalytic α-arylation of ketones; 1 mol % of PdOAc₂; 2 mol % of n-BuPAd₂Con- T version No. Aryl-X (20 C.) Ketone (%) 55

120

100 chloro- aceto- benzene phenone 56

80

66 p- deoxy- chloro- benzoin toluene 57

80

99 p- propio- chloro- phenone toluene 58

80

100 p- 3- chloro- pentan- toluene one 59

80

100 1,2-di- 3- chloro- pentan- benzene one Product 1 Product 2 (mono-Yield^(a)) (bis- Yield^(a)) arylated) (%) arylated) (%)

70

28 deoxy- diphenyl- benzoin methane ./.

65 1,2- diphenyl- 2-p- tolyl- ethanones

97 ./. 1-phenyl- 2-p- tolyl- propan-1- ones

54 not isolated no data 2-p- tolyl- pentan-3- ones

58 not isolated no data 2-(2′- chloro- phenyl)- pentan-3- ones

Examples 60 to 79

[0121] Further Catalysis Examples of the α-arylation of Ketones:

[0122] In a pressure tube (obtainable e.g. from Aldrich), 5 mmol of arylhalide, 6 mmol of ketone, 6 mmol of tripotassium phosphate and asuitable amount of ligand and palladium(II) acetate were added to 5 mlof absolute dioxane under an argon atmosphere. The tube was sealed andsuspended in a silicone oil bath at 100° C. After 20 h it was left tocool to room temperature. The solids were dissolved in 5 ml of CH₂Cl₂and 5 ml of 2 N hydrochloric acid, and 500 mg of diethylene glycoldi-n-butyl ether were added. as internal GC standard. The organic phasewas analyzed by gas chromatography. The products were isolated bydistillation, crystallization from methanol/acetone mixtures or columnchromatography (silica gel, hexane/ethyl acetate mixtures). TABLE 8Reaction of chlorobenzene with acetophenone; 1 mol% of PdOAc₂ No. LigandTemp. Conversion (%) Yield (%) of

deoxybenzoin Yield (%) of

1,2,2- triphenyl- ethanone 60

100 83 16 51 BuPAd₂ 61

100 68 6 44 N,N-dimethyl- aminopropyl- PAd₂ 62

100 72 31 31 phenyl-PCy₂ 63

100 74 33 32 PCy₃ 64

100 50 17 19 o-biphenyl-PCy₂ 65

100 31 17 3 BuPCy₂ 66

100 37 0 19 P(t-Bu)₃ 67

100 44 9 20 Bup(t-Bu)₂ 68

100 17 2 0 PPh₃

[0123] TABLE 9 α-Arylation of ketones; 1 mol % of PdOAc₂; 2 mol % ofn-BuPAd₂ Con- T version No. Aryl-X (° C.) Ketone (%) 69

100

83 chloror- aceto- benzene phenone 70

100

100 p- deoxy- chloro- benzoin toluene 71

120 100

100  48 p- propio- chloro- phenone toluene 72

100

100 p- 1- chloro- indan- toluene one 73

100

42 p- 3- chloro- pentan- toluene one 74

100

100 p- cyclo- chloro- hexan- toluene one 75

100

100 p- aceto- chloro- phenone anisole Product 1 Product 2 (mono-Yield^(a) (bis- Yield^(a) arylated) (%) arylated) (%)

16

51 deoxy- 1,2,2- benzoin tri- phenyl- ethanone ./.

100 1,2- diphenyl- 2-p- tolyl- ethanones

90 38 ./. 1-phenyl- 2-p- tolyl- propan-1- ones

42

32 2-p- 2,2- tolyl-1- bis(p- indanone tolyl)-1- indanone

27 not no data 2-p- isolated tolyl- pentan-3- ones

38 ./. 2-p- tolyl- cyclo- hexanones

25

57 2-p- 2,2-bis- anisyl-1- p-anisyl- phenyl- 1-phenyl- ethanonesethanone

Example 80

[0124] Coupling of Aryl Chlorides with Organozinc Compounds:

[0125] 50 mmol of anhydrous zinc chloride (dissolved in 40 ml of THF)were added at 0° C to a suspension of 50 mmol ofethynyllithium-ethylenediamine complex in 40 ml of THF. After heating toRT for half an hour, the solution was again cooled to 0° C. and 40 mmolof 4-chloroanisole, 0.05 mol % of Pd(OAc)₂ and 0.1 mol % ofbutyldiadamantylphosphine were added. The reaction mixture was stirredat 25 to 50° C. until conversion was complete. 2 M HCl solution was thenadded to the reaction solution. After extraction with ether, washing ofthe ether phase and distillation, 76% of p-methoxyphenylacetylene isobtained.

Example 81

[0126] Coupling with Alkynes:

[0127] 0.005 mol % of Pd(OAc)₂, 0 .01 mol % ofhexyldiadamantyl-phosphine and 1 mol % of Cu(I)I are added to a mixtureof 12 mmol of trimethylsilylacetylene and 10 mmol of4-chloronitrobenzene in 40 ml of diethylamine. The mixture is stirredunder reflux until conversion is complete. The readily volatileconstituents are then removed under vacuum. The residue is dissolved intoluene and washed with water. After chromatography on silica gel, 89%of 1-(4-nitrophenyl)-2-trimethylsilylacetylene is obtained.

Example 82

[0128] Heck Coupling with Ethylene:

[0129] 50 mmol of 6-methoxy-2-bromonaphthalene and 60 mmol of potassiumcarbonate are dissolved in 40 ml of NMP, and 0.001 mol % of Pd(OAc)₂ and0.004 mol % of butyldiadamantyl-phosphine are added. The mixture isplaced under an ethylene pressure of 20 bar and stirred at 130° C. untilconversion is complete. After filtration of the insoluble constituents,washing with alkaline solution and distillation, 92% of6-methoxy-2-vinylnaphthalene is obtained.

Example 83

[0130] Carbonylation Reaction:

[0131] 20 mmol of 6-methoxy-2-bromonaphthalene and 30 mmol oftriethylamine are dissolved in 30 ml of 1-butanol, and 0.05 mol % ofPd(OAc)₂ and 0.1 mol % of butyldiadamantylphosphine are added. Themixture is placed under a CO pressure of 3 bar and stirred at 130° C.until conversion is complete.

[0132] After filtration of the insoluble constituents, washing withalkaline solution and distillation, 94% of butyl6-methoxy-2-naphthalenecarboxylate is obtained.

1. Novel phosphine ligands of formulae Ia and Ib: (adamantyl)₂P(alkyl)  Ia (adamantyl)₂P(alkylene′)P(adamantyl)₂   Ib in which adamantyl is anadamantyl radical (IIa, IIb) bonded to the phosphorus atom in the 1- or2-position:

alkyl is an ethyl, n-propyl, i-propyl or n-butyl group or a linear orbranched C₅-C₁₈ alkyl group, and alkylene′ is a bridging methylene,1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylenebridge, 1,2-diphenylene, 2,2′-substituted 1,1′-binaphthyl or aferrocenyl bridge, where the alkyl group, the alkylene′ group and theadamantyl radical independently of one another can have, in addition tohydrogen atoms, up to 10 substituents which independently of one anotherare O-alkyl(C₁-C₈), OH, OCO-alkyl(C₁-C₈), O-phenyl, phenyl, aryl,fluorine, NO₂, Si-alkyl(C₁-C₈)₃, CN, COOH, CHO, SO₃H, NH₂,NH-alkyl(C₁-C₈), N-alkyl(C₁-C₈)₂, P(alkyl(C₁-C₈))₂, P(aryl)₂,SO₂-alkyl(C₁-C₆), SO-alkyl(C₁-C₆), CF₃, NHCO-alkyl(C₁-C₄),COO-alkyl(C₁-C₈), CONH₂, CO-alkyl(C₁-C₈), NHCHO, NHCOO-alkyl(C₁-C₄),CO-phenyl, COO-phenyl, CH═CH—CO₂-alkyl(C₁-C₈), CH═CHCOOH, PO(phenyl)₂,PO(alkyl(C₁-C₄) )₂, PO₃H₂, PO(O-alkyl(C₁-C₆) )₂ or SO₃(alkyl (C₁-C₄)),aryl being an aromatic with 5 to 14 ring carbon atoms, it being possiblefor one or more ring carbon atoms to be replaced by nitrogen, oxygenand/or sulfur atoms to give a heteroaromatic with 1 to 13 ring carbonatoms, and it being possible for both the alkylene′ group and theadamantyl radical independently of one another to carry (C₁-C₈) alkylsubstituents.
 2. Novel phosphine ligands according to claim 1 in whichadamantyl is an adamantyl radical (IIa, IIb) bonded to the phosphorusatom in the 1- or 2-position, alkyl is an ethyl, n-propyl, i-propyl orn-butyl group or a linear or branched C₅-C₁₂ alkyl group, and alkylene′is a bridging 1,2-ethylene, 1,3-propylene or 1,4-butylene bridge,1,2-diphenylene, 2,2′-substituted 1,1′-binaphthyl or a ferrocenylderivative, where the alkyl group, the alkylene′ group and the adamantylradical independently of one another can have, in addition to hydrogenatoms, up to 5 substituents which independently of one another areO-alkyl(C₁-C₈), OH, OCO-alkyl(C₁-C₈), O-phenyl, phenyl, aryl, fluorine,Si-alkyl(C₁-C₈)₃, COOH, SO₃H, NH₂, NH-alkyl(C₁-C₈), N-alkyl₂(C₁-C₈),P(alkyl(C₁-C₈))₂, P(phenyl)₂, CF₃, NHCO-alkyl(C₁-C₄), COO-alkyl(C₁-C₈),CONH₂, CO-alkyl(C₁-C₈), COO-phenyl, PO(phenyl)₂, PO(alkyl(C₁-C₄))₂,PO₃H₂ or PO(O-alkyl(C₁-C₆))₂, aryl being an aromatic with 5 to 14 ringcarbon atoms, it being possible for one or more ring carbon atoms to bereplaced by heteroatoms from the group comprising nitrogen, oxygen andsulfur atoms to give a heteroaromatic with 1 to 13 ring carbon atoms,and it being possible for both the alkylene′ group and the adamantylradical independently of one another to carry (C₁-C₈) alkylsubstituents.
 3. Novel phosphine ligands according to claim 1 or 2 inwhich adamantyl is an adamantyl radical (IIa, IIb) bonded to thephosphorus atom in the 1- or 2-position, alkyl is an ethyl, n-propyl,i-propyl or n-butyl group or a linear or branched C₅-C₁₂ alkyl group,and alkylene′ is a bridging 1,2-ethylene, 1,3-propylene or 1,4-butylenebridge, where the alkyl group, the alkylene′ group and the adamantylradical independently of one another can have, in addition to hydrogenatoms, up to 3 substituents which independently of one another can beO-alkyl(C₁-C₈), OH, OCO-alkyl(C₁-C₈), O-phenyl, phenyl, COOH, SO₃H, NH₂,P(alkyl(C₁-C₈))₂, P(phenyl)₂, COO-alkyl(C₁-C₈), CONH₂ or PO(phenyl)₂, itbeing possible for both the alkylene′ group and the adamantyl radicalindependently of one another to carry (C₁-C₈) alkyl substituents. 4.Process for the preparation of phosphine ligands of formulae Ia and Ib:(adamantyl)_(n)P(alkyl)_(m)   Ia(adamantyl)_(o)(alkyl)_(q)P(alkylene′)P(adamantyl)_(r)(alkyl)_(s)   Ibin which adamantyl is an adamantyl radical (IIa, IIb) bonded to thephosphorus atom in the 1- or 2-position:

alkyl is a C₁ to C₁₈ alkyl group, and alkylene′ is a bridging methylene,1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylenebridge, 1,2-diphenylene, 2,2′-substituted 1,1′-binaphthyl or aferrocenyl bridge, where the alkyl group, the alkylene′ group and theadamantyl radical independently of one another can have, in addition tohydrogen atoms, up to 10 substituents which independently of one anotherare C₁ to C₈ alkyl, O-alkyl (C₁-C₈), OH, OCO-alkyl(C₁-C₈), O-phenyl,phenyl, aryl, fluorine, NO₂, Si-alkyl(C₁-C₈)₃, CN, COOH, CHO, SO₃H, NH₂,NH-alkyl(C₁-C₈), N-alkyl(C₁-C₈)₂, P(alkyl(C₁-C₈))₂, P(aryl)₂,SO₂-alkyl(C₁-C₆), SO-alkyl(C₁-C₆), CF₃, NHCO-alkyl(C₁-C₄),COO-alkyl(C₁-C₈), CONH₂, CO-alkyl(C₁-C₈), NHCHO, NHCOO-alkyl(C₁-C₄),CO-phenyl, COO-phenyl, CH═CH—CO₂-alkyl(C₁-C₈), CH═CHCOOH, PO(phenyl)₂,PO(alkyl(C₁-C₄))₂, PO₃H₂, PO(O-alkyl(C₁-C₆))₂ or SO₃(alkyl(C₁-C₄)), arylbeing an aromatic with 5 to 14 ring carbon atoms and it being possiblefor one or more ring carbon atoms to be replaced by nitrogen, oxygenand/or sulfur atoms to give a heteroaromatic with 1 to 13 ring carbonatoms, where n is a number between 1 and 3 and m is a number between 0and 2, it being necessary to satisfy the condition n+m=3, and where oand r are the number 1 or 2 and q and s are the number 0 or 1, it beingnecessary to satisfy the conditions o+q=2 and r+s=2, characterized inthat the phosphine ligands are prepared by reacting adihalogenoadamantylphosphine or halogeno-diadamantylphosphine withmetal-organic reagents.
 5. Process for the preparation of phosphineligands of formulae Ia and Ib according to claim 4, characterized inthat the novel phosphine ligands are prepared by reacting alkali metaladamantylphosphides or alkali metal diadamantylphosphides with organicelectrophiles such as alkyl halides or pseudohalides, aldehydes orepoxides.
 6. Use of phosphine ligands of formulae Ia and Ib:(adamantyl)_(n)P(alkyl)_(m)   Ia(adamantyl)_(o)(alkyl)_(q)P(alkylene′)P(adamantyl)_(r)(alkyl)_(s)   Ibin which adamantyl is an adamantyl radical (IIa, IIb) bonded to thephosphorus atom in the 1- or 2-position:

alkyl is a C₁ to C₁₈ alkyl group, and alkylene′ is a bridging methylene,1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylenebridge, 1,2-diphenylene, 2,2′-substituted 1,1′-binaphthyl or aferrocenyl bridge, where the alkyl group, the alkylene′ group and theadamantyl radical independently of one another can have, in addition tohydrogen atoms, up to 10 substituents which independently of one anotherare C₁ to C₈ alkyl, O-alkyl (C₁-C₈), OH, OCO-alkyl(C₁-C₈), O-phenyl,phenyl, aryl, fluorine, NO₂, Si-alkyl(C₁-C₈)₃, CN, COOH, CHO, SO₃H, NH₂,NH-alkyl(C₁-C₈), N-alkyl(C₁-C₈)₂, P(alkyl(C₁-C₈))₂, P(aryl)₂,SO₂-alkyl(C₁-C₆), SO-alkyl(C₁-C₆), CF₃, NHCO-alkyl(C₁-C₄),COO-alkyl(C₁-C₈), CONH₂, CO-alkyl(C₁-C₈), NHCHO, NHCOO-alkyl(C₃-C₄),CO-phenyl, COO-phenyl, CH═CH—CO₂-alkyl(C₁-C₈), CH═CHCOOH, PO(phenyl)₂,PO(alkyl(C₁-C₄))₂, PO₃H₂, PO(O-alkyl (C₁-C₆) )₂ or SO₃ (alkyl (C₁-C₄)),aryl being an aromatic with 5 to 14 ring carbon atoms and it beingpossible for one or more ring carbon atoms to be replaced by nitrogen,oxygen and/or sulfur atoms to give a heteroaromatic with 1 to 13 ringcarbon atoms, where n is a number between 1 and 3 and m is a numberbetween 0 and 2, it being necessary to satisfy the condition n+m=3, andwhere o and r are the number 1 or 2 and q and s are the number 0 or 1,it being necessary to satisfy the conditions o+q=2 and r+s=2, ascatalysts in combination with transition metal complexes or transitionmetal salts of subgroup VIII of the Periodic Table of the Elements, forthe catalytic preparation of dienes or arylated olefins (Heckreactions), biaryls (Suzuki reactions), α-aryl ketones and/or aminesfrom aryl halides or vinyl halides, in catalytic carbonylations of arylhalides, alkynylations with alkynes (Sonogashira couplings) and crosscouplings with metal-organic reagents, for the preparation ofarylolefins, dienes, diaryls, benzoic acid derivatives, acrylic acid.derivatives, arylalkanes, alkynes and amines, wherein the ligands areadded in situ to the appropriate transition metal precursor compounds orused direct as transition metal phosphine complexes.
 7. Use according toclaim 6, characterized in that the transition metals used are the metalspalladium, nickel, platinum, rhodium, iridium, ruthenium and cobalt. 8.Use according to claim 6 or 7, characterized in that the transitionmetal compounds used are palladium or nickel compounds, preferablypalladium compounds.
 9. Use according to claim 6, characterized in thatpreviously prepared, defined mono-, di-, tri- or tetraphosphinecomplexes of the transition metals according to claim 7 or 8 are usedfor the catalytic reactions.
 10. Use according to one of the precedingclaims, characterized in that the ligands are used at temperatures of 20to 200° C.
 11. Use according to claim 10, characterized in that thetemperature is kept at 30 to 180° C., preferably at 40 to 160° C. 12.Use according to one of the preceding claims, characterized in that, inthe catalytic application, the phosphine ligand is used in excessrelative to the transition metal in a ratio of transition metal toligand of 1:1 to 1:1000.
 13. Use according to claim 12, characterized inthat the ratio of transition metal to ligand is 1:1 to 1:100.